International Journal of Engineering and Applied Sciences (IJEAS)
ISSN: 2394-3661, Volume-3, Issue-1, January 2016
Batch Adsorption Kinetics of Zinc Ions Using
Activated Carbon from Waste Nigerian Bamboo
Ademiluyi F.T, Alex Abidde
Abstract Batch adsorption kinetics of Zinc ions using
activated carbon from waste Nigerian bamboo was investigated.
The bamboo was cut into sizes, washed, dried and carbonized
at 300oC-500oC. It was then activated at 800oC using nitric
acid. The effect of contact time on the adsorption of zinc ions in
aqueous solution was also investigated and were found to
significantly affect the adsorption capacity of zinc ions . The
adsorption process fitted well into the Freundlich, and
Langmuir isotherm models indicating a monolayer formation
over the surface of the material. Langmuir isotherm had
monolayer saturation capacity of 250 mg/g of zinc ions
adsorbed per g of bamboo activated carbon and high adsorption
intensity of 1.579. In order to determine the mechanism of
sorption, kinetic data were modeled using the pseudo first order
, pseudo second order kinetic equations, and intra-particle
diffusion model. The pseudo second order equation was the best
applicable model to describe the sorption process. Hence the
pseudo second order kinetic reaction is the rate controlling step
with some intra particle diffusion taking place during the
adsorption.
Index Terms Nigerian Bamboo, Activated Carbon,
Kinetics, Zinc ions, Adsorption Isotherm.
I. INTRODUCTION
Zinc is one of the heavy metals considered toxic to plants,
invertebrates, and even vertebrate fish. Though zinc is useful
to man but excess amount of zinc ions in waste waters may
cause zinc toxicity which could lead to severe hemolytic
anemia, liver and kidney damages; vomiting and diarrhea [1].
Zinc oxide is widely used as a white pigment in paints, and as
a catalyst in the manufacture of rubber [2]. High release of
zinc ions into the environment is also toxic to agricultural
activities, sediment entrainment and groundwater. As a result
of this inevitable development due to industrial discharge, a
few techniques for the removal of these heavy metals (lead,
zinc, zinc, Nickel, chromium, mercury, cadmium, aluminum,
manganese and cobalt) were introduced by concerned
researchers for the removal of these heavy metals from
untreated water. These methods are reverse osmosis, ultra
filtration, nano-filtration, coagulation, sedimentation,
adsorption, etc. Though, it was discovered that these methods
have been proved to have a lot of disadvantages which
includes cost of operation and production of post sludge.
Among the aforementioned treatment methods, adsorption
had been reported as an efficient and economic option [3,4]
especially when the source of adsorbent is economical.
Ademiluyi F.T, Department of Chemical/Petrochemical Engineering.
Faculty of Engineering, Rivers State University of Science and Technology,
Nkpolu, Port Harcourt, Nigeria
Alex Abidde, Department of Chemical/Petrochemical Engineering.
Faculty of Engineering, Rivers State University of Science and Technology,
Nkpolu, Port Harcourt, Nigeria
95
Adsorption is one of the cheap and most effective methods in
water purification and activated carbon is preferred adsorbent
that is wildly used to treat waste water containing different
classes or types of metal ions. Activated carbon has the
tendency of adsorbing large and small dissolved organic
molecules such as gases, chemicals and metal ions.
Different adsorbent has been reported for the removal of zinc
ions in solution. High removal of zinc from water was
achieved using acid treated Carbon Nanofibers [ 1 ]. Results
of the study showed that, 97 % of zinc was removed by using
COOH-CNFs a Carbon Nanofibers at pH 7, 150 rpm, and 2
hours. Process optimization of the removal of Zn (II) by
activated carbon prepared from rice husk using chemical
activation was also reported. [5]. The adsorption of Zinc,
Cadmium and Nickel from aqueous solution using ground
water sludge (GWS) as the adsorbent [6]. In this study, the
adsorbent concentration (GWS) were varied from 250 mg/L
to 400mg/L and agitated with aqueous solutions of heavy
metal for 1 hr, 3hrs, 6 hrs, and 24 hrs contact time. It was
found that adsorption of metal ions also increased with longer
contact time and higher adsorbent dosages. The removal
efficiencies for Cd, Ni and Zn at adsorbent concentration of
3000 mg/L, 3,500 mg/L and 4,000 mg/L, were found to be
91.6%, 73.8% and 69% respectively.
Batch sorption of Cu2+ and Zn2+ ions in aqueous solutions
was investigated under different pH value, adsorption time,
original content of metal ions, sorbent amount, and
temperature using activated carbon, prepared from Typha
latifolia [7] . Nigerian bamboo has been reported to be
effective in the removal of heavy metals [8]. but the kinetics
of the zinc ions from aqueous solution using activated carbon
from Nigerian bamboo has not been studied.
Therefore the objectives of these work is to study the kinetics
of the removal of zinc ions using activated carbon from
Nigerian bamboo.
II. MATERIALS AND METHODS
A. Materials
The following materials and apparatus were used for this
work: waste Nigerian based bamboo from a construction site
on campus. Nitric acid was used as activating agents, A
pyrolytic reactor was used for carbonization with condenser.
Other materials used are heating mantle, desiccators,
crucibles, funnels, and filter papers. Two electronic weighing
balance, Ohaus top loading balance (+0.01) was used to
weigh the bamboo before pyrolysis, while a more sensitive
electronic analytical weighing balance (+0.001, Adams AFP
360L) was used for other analysis, retort stand, thermocouple
with temperature sensor, spatula, crusher, sieves, measuring
cylinders, and petri dish.
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 Batch Adsorption Kinetics of Zinc Ions Using Activated Carbon from Waste Nigerian Bamboo

B. Carbonization The amount of zinc ions adsorbed at equilibrium, Q eq (mg/g)

2kg of waste bamboo was cut into small sizes, washed, and was determined using equation
dried. They were carbonized differently in a pyrolytic reactor (Co Ce ) V metal ion uptake (mg)
at about 300500C for about two hours after which the
Qe
m g of carbon (1)
charred products were allowed to cool to room temperature.
The charred material was crushed and sieved.
and the percent zinc ion adsorbed (%) was computed as
C. Chemical Activation follows [11] :
The carbonised waste bamboo were weighed separately and
poured in different beakers containing known quantity of (Co C )
trioxonitrate (v) acid. The best concentrations of the acid used
for activation were already determined before this study [9]. Percent adsorption (%) =
Co x 100 (2)
The content of the beakers was thoroughly mixed until a paste
was formed. The paste of the sample were then where Co and Ce are the initial and equilibrium
transferred to crucibles and were placed in a Muffle furnace concentrations (mg/L), V volume of solution, m the weight of
and heated at 800C for two hours. The activated sample activated carbon (g) and C the solution concentration at the
were then cooled at room temperature, washed with distilled end of adsorption
water to a pH of 6-7, and dried in an oven at 105C for three E Adsorption Isotherms modeling
hours. The final products were sieved to same particle size, The most commonly used isotherms in adsorption studies was
kept in an air tight polyethylene bags, ready for use used to fit the experimental adsorption data namely :
Langmuir, and Freundlich Isotherms
The Langmuir isotherm was expressed as [12]:
Ce 1 a Ce
L
Qe KL KL
(3)
where Qe is the amount of zinc ion adsorbed per unit mass of
adsorbent (mg/g) at equilibrium, Ce is the equilibrium
concentration of the adsorbate (mg/L)
KL = A constant related to the affinity between the adsorbent
and the adsorbate (L/mg)
Fig 1 Pieces of Nigerian waste bamboo before, after Qmax= KL/ aL = The theoretical monolayer saturation
carbonization and after activation. capacity.

The values of Qmax and KL can be determined by plotting

D. Adsorption of Zinc ions in Aqueous Solution on
Ce / Qe versus Ce
Activated Carbons
One of the most important parameter in the Langmuir
Stock solution of zinc solution was prepared by dissolving 1g isotherm model is the seperation factor RL which is a
of salt containing zinc II ions into 1 litre of distilled water. 1g dimensionless factor defined as [13]
of activated carbon was measured and poured into 100ml of 1
the zinc salt solution inside the flask. The adsorption was RL
carried out initially for 15mins and filtered at room 1 a L Co
(4)
temperature of 30oC. The above procedure was done for 30 where: Co is the initial adsorbate concentration of zinc ions
minutes, 45 minutes, 60 minutes, 90 minutes, 120 minute and and aL is the Langmuir constant related to the energy of
180 minutes till equilibrium was reached and was repeated for adsorption. The values of RL indicate the nature of the
different concentration of zinc ions in solution. The isotherm to be either unfavorable (RL> 1) , favorable (0 < RL
adsorption of zinc in aqueous solution on bamboo activated < 1), linear (RL = 1), or irreversible (RL = 0).
carbon was carried out by studying the effect of various
physicochemical parameters such as particle size, carbon The linear form of the Freundlich isotherm is the earliest
dosage, initial concentration , contact time on the adsorption known relationship describing the adsorption equation and is
process. often expressed as
The amount of zinc ions in solution (i.e., Zn2+) was
1
determined using conductometric method from the filtrate Log Qe Log K f Log C e
after adsorption using waste Nigerian based bamboo. As n (5)
described in the work of Banjonglaiad et al., [10] at low Kf = The Freundlich constant related to the adsorption
concentrations, conductivity is linearly related to the different capacity
metal ion concentrations so that if just one metal is present its 1/n= The Freundlich constant related to the adsorption
concentration is readily established through calibration. intensity.
Hence a calibration curve of zinc ion concentration versus F Kinetic study
conductivity was first prepared for each metal ion, before the Three kinetic models were used in this study to model the
kinetic study. adsorption of zinc II ion on bamboo activated carbon namely:

96 www.ijeas.org
 International Journal of Engineering and Applied Sciences (IJEAS)
ISSN: 2394-3661, Volume-3, Issue-1, January 2016
pseudo first order, pseudo second order and the intra particle
diffusion models.
a) The pseudo first order considers the rate of occupation of
adsorption sites to be proportional to the number of
unoccupied sites.
ln (Qe -Qt ) = ln Qe - K t (6)
b) The Pseudo Second order kinetic model for adsorption of
zinc is expressed as [14]:
t 1 t
2
Qt k2Qe Qe
(7)
Intra -particle diffusion may be the rate determining step in
batch adsorption process the uptake of adsorbate varies with
the square root of the adsorption time [14] .
where, Qe is the mass of metal adsorbed at equilibrium
(mg/g), Qt (mg/g) is the mass of metal adsorbed at time t and
K is the first order reaction rate constant (L/min). A straight
line of ln (Qe - Qt) verses t indicates the application of the first
order kinetic model .
so that
Qt = k2 t0.5+C (8)
A linear plot of Qt versus t0.5 shows that the adsorption
mechanism follows intra -particle diffusion and if the intra
-particle diffusion is the rate controlling step , the line would
passes through the origin.
III. RESULTS AND DISCUSSION
A. Effect of Contact Time on Batch Adsorption of Zinc ions
in Aqueous Solution
Figure 2 shows the effect of contact time on the adsorption of
zinc ions solution using activated carbon from Nigerian
bamboo. The concentrations of zinc ions in solution was
varied from 28mg/L to 227mg/L and batch adsorption was
carried out with 1g of activated bamboo. The percentage of
zinc ions adsorbed increased with time until equilibrium was
reached for each concentrations. It is therefore evident from
Fig 2 that at low concentration ranges the percent adsorption
is high because of the availability of more active sites.
At higher concentration of metal ion more and more surface
sites are covered, the capacity of the adsorbent get exhausted
due to non-availability of active surface sites. This leads to a
fall in the percentage of metal ion adsorbed at higher
concentration. It was observed that the percentage
adsorption of zinc ion rapidly reached equilibrium at 30
minutes of contact for 28mg/L concentration, it increased to
100% implied that zinc ion was completely removed from
aqueous solution at this concentration
97
Figure 2 Effect of Contact Time on the Adsorption of Zinc
(II) ions using waste Nigerian Bamboo Carbon
This is because at this time equilibrium is established. The
delay in equilibrium condition at higher concentrations may
be attributed to the few available sites of adsorptions. Beyond
this optimum contact time it is evident that the surface of the
adsorbent becomes more and more saturated due to the
availability of many active sites.
B. Adsorption Isotherms
C. Langmuir Adsorption Isotherm for Zinc ion
Fig 6 shows the Langmuir adsorption isotherm for the
adsorption of Zinc ions on bamboo activated carbon. the
equilibrium concentration of zinc ions in solution (Ce) varies
linearly with the ratio of the equilibrium concentration and
the amount of zinc ions adsorbed (Ce/Qe). The linearity of the
plot shows that Langmuir isotherm model can be used to
predict the sorption of zinc ions on bamboo activated carbon.
The Langmuir model assumes that the uptake of metal ions
occurs on a homogeneous surface by monolayer adsorption
without any interactions between adsorbed ions [15]. The
Langmuir model parameters and the statistical aspect of the
adsorption data is presented in Table 2 and the correlation
coefficient R2 of 0.995 which reveals that the isotherm is
consistent with Langmuir model. The adsorption capacity
Qmax for zinc represents a practical limiting adsorption
capacity when the surface is fully covered with heavy metal
ions and assists in the comparison of adsorption performance
[11].
The adsorption capacity Qmax of activated carbon from
bamboo was 250 mg/g of carbon. It was obtained from the
reciprocal of the slope of Fig 3. This value is higher than the
value obtained by Kalavathy et al., [16], in which Qmax value
of 22.03mg/g was obtained during the removal of Zn from
aqueous solution using activated carbon from Hevea
brasiliensis. It was also higher than the value obtained by
Surya and Ramachandra [11] with a Qmax of 38.2mg/g at
30oC during the adsorption of zinc ions on Shorea Robusta
Leaf Litter using phosphoric acid impregnation. The
maximum adsorption capacity observed during the
adsorption of Zn2+ ions onto biogenic elemental selenium
nanoparticles (BioSeNPs) was 60 mg of Zinc adsorbed per g
[18] .
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 Batch Adsorption Kinetics of Zinc Ions Using Activated Carbon from Waste Nigerian Bamboo
Fig 3 Langmuir adsorption isotherm for the adsorption of
Zinc ions on bamboo activated carbon
The separation factor (RL) was determined from equation 4,
the values were between 0.053 to 0.309 for adsorbate
concentrations between 28 mg/L to 227mg/L. Since RL is less
than 1 for all the concentrations it means that adsorption
process is favorable.
D. Freundlich Adsorption Isotherm for Zinc ion
The batch adsorption isotherm of zinc ions on bamboo
activated carbon at 30 oC is presented in Fig 4 . The log of Qe
amount of zinc adsorbed at equilibrium was plotted against
the log of the equilibrium concentration Ce of the metal ion
adsorbed. The adsorption capacity Kf and the adsorption
intensity 1/n were obtained directly from the slopes and
intercepts of the linear plot. The linearity of the plot and high
correlation coefficient R2 obtained (0.995) reveals that the
isotherm is consistent with Freundlich model . The value of
adsorption intensity i.e n = 1.579 from Table 2 is more than
one for bamboo activated carbon , indicating the adsorption
zinc ion using bamboo activated carbon is more of
chemisorptions than physical adsorption .
Fig 4 Freundlich Isotherm adsorption of zinc from aqueous
solution using activated carbons from bamboo
Table 2 Constants and values from Isotherms Models for
adsorption of zinc from aqueous solution using activated
carbons from waste Nigerian bamboo
98
S/No Isotherm Constants Values
1. langmuir
Qmax= KL/aL (mg/g) 250
KL (L/mg) 19.608
R2 0.998
2. Freundlich
n 1.579
Kf 19.498
R2 0.995
E. Adsorption Kinetic Models
The kinetic plots for the adsorption of zinc II ions on activated
carbon from Bamboo using the pseudo first order, pseudo
second order and the intra particle diffusion models at
different concentrations is presented in Figures 5, 6 and 7. All
concentration of zinc ions in solution below 100mg/L were
not captured in Fig 5 and Fig 7 for the kinetic plot for first
order and Intra particle diffusion kinetic models because the
values were too small. The Pseudo first order kinetic and Intra
particle diffusion kinetic models can only be used for zinc at
high concentrations, unlike the Pseudo second order kinetic
model for the batch adsorption of zinc ions shown in Fig 6
which accommodates wide range of zinc ion concentrations in
aqueous solution as shown in Fig 6.
Fig 5 Pseudo first order kinetic plot for the batch adsorption
of zinc ions at different concentrations of adsorbate at 30oC
Figures 6 also shows that the concentration of adsorbate
affected the adsorption and diffusion process greatly since the
slope and intercept are not the same at the different
concentrations. The pseudo second order kinetic model gave
a higher correlation coefficient R2 at all concentration than
the pseudo first order and the intra particle diffusion models
as shown in Fig 6.
The linearity of plot of Qt versus t0.5 in Fig 7 shows that the
adsorption mechanism follows intra -particle diffusion but the
line of the plot in Fig 11 did not pass through the origin. The
values obtained from the intercept (64.09, 76.19, and 80.46)
of the intra particle diffusion kinetic model at different
adsorbate concentrations are not the same as shown in Fig 7
and did not pass through the origin which indicated intra
-particle diffusion is not the rate controlling step.
www.ijeas.org
 International Journal of Engineering and Applied Sciences (IJEAS)
ISSN: 2394-3661, Volume-3, Issue-1, January 2016
Fig 6 Pseudo second order kinetic plot for the batch
adsorption of zinc ions at different concentrations of
adsorbate at 30 oC
Fig 7 Intra particle diffusion kinetic model plot for the batch
adsorption of zinc ions at different concentrations of
adsorbate at 30oC
Thus pseudo second order kinetic is the rate controlling step.
Also the values of the intercept of Fig 7 at the different
concentrations gives an idea of the thickness of the boundary
layer, the larger the intercept the thicker the boundary layer
effect [17] . The values obtained from the intercept from Fig 7
(64.09-80.46) are significant, which revealed that the
boundary is thick. Hence the pseudo second order kinetic
reaction is the rate controlling step with some intra particle
diffusion taking place.
IV. CONCLUSION
Zinc II ions batch adsorption kinetics from aqueous solution
using activated carbon from waste Nigerian based bamboo
has been investigated. The amount of zinc II ions adsorbed
was found to vary significantly with contact time. The
adsorption process fitted well into Langmuir, and Freundlich
isotherms models. The monolayer saturation capacity of 250
mg of zinc II ions adsorbed per g of bamboo activated carbon
was obtained and found to be higher than monolayer
saturation capacity of other adsorbent used for zinc II ions
adsorption. Adsorption kinetics was modelled using the
99
pseudo first order , pseudo second order kinetic equations,
and intra-particle diffusion models. sorption kinetics showed
good agreement with experimental data. The pseudo second
order kinetic reaction is the rate controlling step with some
intra particle diffusion taking place. The high adsorption
intensity of bamboo activated carbon and its affinity for zinc
II ions can help solve many adsorption challenges in the
industry and in water purification processes.
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